Hybrid thermoplastic gels and their methods of making

ABSTRACT

Methods, compositions, apparatuses, and systems are provided for a hybrid thermoplastic gel or sealant. The methods comprise providing (a) a base polymer having at least one functional group capable of crosslinking, (b) a functionalized extender, and (c) heat, and reacting the base polymer and functionalized extender in the presence of the heat to form the hybrid thermoplastic gel. The gel composition may comprise 5-40 wt % of a base polymer, 60-95 wt % of a functionalized extender, and 0-10 wt % of a crosslinker. A closure or interconnect system may comprise a housing, a cable, and a hybrid thermoplastic gel or sealant. A telecommunications apparatus may comprise a telecommunications component and a sealant that forms a seal with the telecommunications component. The sealant may comprise a sealant material having a first range of elongation followed by a second range of elongation.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 61/681,940, filed Aug. 10, 2012, which is incorporatedherein by reference.

BACKGROUND

In today's modern electrical and electronic devices, as well as in otheruses such as fiber optic connections, sealants are often used forinsulation, for protection against water, corrosion and environmentaldegradation, optical index matching, and thermal management. Prior tonow, a number of sealants including gels have been known, however,processing gels in a cost effective, efficient, and effective manner hasbeen a challenge.

As technology progresses, sealants will be subjected to increasinglyhigher temperature environments and more demanding performancerequirements. There has been, and there presently exists, a need forhigh performance sealants to meet these demands. For example, there isan increasing need for high service gel sealants for use in outdoorenergy transmission applications and for use near engine compartments.

In particular, closure systems are used to protect internal componentsfrom degradation caused by external environments. For example, internalcomponents such as fiber optic cables and copper cables are oftenenclosed in closure systems. Examples of commercially available closuresystems include the Outdoor Fiber Drop Repair (OFDR), the Outdoor FiberDistribution Closure (OFDC), and the Fiber optic Infrastructure SystemTechnology (FIST), available from Tyco Electronics, Kessel-Lo, Belgium.In particular, the OFDR Closure is used to break out fibers from alooped fiber optic cable to connect users such as business customers orpersons in multiple or single living units. These types of closures canbe used in aerial, pedestal, and underground environments. Other closuresystems are commercially available for use with communication and energytransmission cables.

Closure systems typically include internal components such as fiberorganizers, cable seals and termination devices, drop cable seals for anumber of drops with drop cable termination devices, and universalsplice holders for a number of splices. These internal components may besubject to environmental factors such as varying moisture levels, heatand cold, and exposure to other chemical substances. The closure systemsare preferably protected from damage with a sealant of some sort.Conventional sealants, however, suffer from a number of drawbacks thatmake them unsuitable for certain closure systems.

Sealants are often used for insulation and for protection against water,corrosion and environmental degradation, and for thermal management.Prior to now, a number of sealants have been known; however, currentlyavailable sealants have certain drawbacks and disadvantages that makethem inadequate for specific uses and for use in contact with certainmaterials. In particular, there is an unmet need for sealants that aresuitable for fiber optic and electronic closure systems.

Suitable sealing systems for closures are needed for use with a varietyof different cables. For examples, a sealing system is needed for cablestermed Low Smoke Zero Halogen (“LSZH”), also known as Low Smoke HalogenFree (“LSHF”), Low Smoke Zero Halogen (“LSOH”), and Zero Halogen LowSmoke (“OHLS”) among other things.

LSZH cables are characterized by containing no halogenatedflame-retardants, and produce relatively limited amounts of smoke whenexposed to sources of heat such as a flame or heated wires. LSZH cablesprovide an alternative to the frequently used polyethylene, PVC, orthermoplastic urethane coatings. Polyethylene, PVC, or thermoplasticurethane, when they contain halogens, may produce hazardoushalogen-containing compounds such as HCl or HBr gas. An improvement tocurrent LSZH cable closure systems is needed to enhance performance inenvironmentally sensitive environments.

Traditionally, thermoplastic elastomer gels (TPEGs) have been used assealants in certain applications, including LSZH closure systems, due totheir unique properties. TPEGs have provided many years of reliablein-field performance for applications requiring a low maximum servicetemperature of approximately 70° C. TPEGs may comprise a styreneethylene/butylene styrene (“SEBS”) triblock copolymer swollen with amineral oil softener. While the thermoplastic nature of these gelsallows for easy production, it limits the upper service temperature dueto creep and flow as in-field ambient temperatures approach the styreneglass transition. Research has been aimed at increasing the upperservice temperature of these gels through chemically crosslinking thegel network in order to form a thermoset gel structure. For example,oil-swelled acid/anhydride modified maleic anhydride SEBS gels have beencovalently crosslinked using small molecule crosslinkers like di- andtriamines, EP 0879832A1, as well as with some metal salts, D. J. St.Clair, “Temp Service,” Adhesives Age, pp. 31-40, September 2001.Crosslinked polymers are known to increase thermal stability, toughness,and chemical resistance compared to their base, or uncrosslinkedpolymers. However, crosslinked polymers are also known to often beintractable, making them difficult to reprocess or recycle.

A problem, however, with thermoplastic gels used as sealants, and inclosure systems in general, is that they often contain high amounts ofmineral oil. One observed problem is that certain flame retardantadditives, such as ethylene vinyl acetate (EVA), may bond to the mineraloil and make the jacket cable of the closure system fairly rigid anddegrade, making the closure susceptible to leaking oil. The oil in thesegels may leak from the gel and cause deterioration, discoloring, ordegradation of the cable in the closure system. In some extreme cases, acable may even snap under compression due to the damage done by the oilleaking from the thermoplastic gel. Accordingly there exists an unmetneed for gels, sealants, and closure systems with suitable hardness,viscoelastic properties, low permanent set or compression set, long-termperformance (e.g., >20 years), amongst other properties, includingcompatibility with EVA and LSZH cables.

BRIEF SUMMARY

In one embodiment, a method is provided for making a hybridthermoplastic gel comprising providing a base polymer having at leastone functional group capable of crosslinking, providing a functionalizedextender, and providing heat. The method further comprises reacting thebase polymer and functionalized extender in the presence of the heat toform the hybrid thermoplastic gel.

The method may further comprise providing a crosslinker having multiplefunctional groups that are compatible and willing to react with thefunctional groups in the base polymer or functionalized extender. Also,the method may further comprise providing at least one additive selectedfrom the group consisting of: flame retardants, coloring agents,adhesion promoters, stabilizers, fillers, dispersants, flow improvers,plasticizers, slip agents, toughening agents, and combinations thereof.

Additionally, the method may further comprise providing between 0.1 wt %and 5 wt % of a stabilizer. In some embodiments, the stabilizer isselected from the group consisting of antioxidants, acid-scavengers,light and UV absorbers/stabilizers, heat stabilizers, metaldeactivators, free radical scavengers, carbon black, antifungal agents,and mixtures thereof.

In some embodiments the base polymer comprises a styrenic blockcopolymer. The styrenic block copolymer may be astyrene-ethylene/butylene-styrene, styrene-ethylene/propylene-styrenecopolymer or styrene butadiene styrene (SBS). In other embodiments, thebase polymer comprises a maleated base polymer.

In some embodiments, the functionalized extender comprises a singleolefin at a terminal position on the extender. In one embodiment, thefunctionalized extender is a polyisobutylene. In another embodiment, thefunctionalized extender is a maleated extender. The maleated extendermay be a maleated polyisobutylene.

In certain embodiments the gel comprises one or more of the followingproperties: (a) hardness between 80 g and 300 g; (b) a stress relaxationbetween 20% and 65% when the gel is subjected to a deformation of 50% ofits original size; (c) a compression set between 4% and 20% after 50%strain has applied to the gel for 1000 hours at 70° C.; and (d) lessthan 10% oil bleed out after being under compression of 1.2 atm for 60days at 60° C.

In another embodiment, a hybrid thermoplastic gel is provided comprising5-40 wt % of a base polymer having at least one functional group capableof crosslinking. The gel further comprises 60-95 wt % of afunctionalized extender. The gel further comprises 0-10 wt % of acrosslinker having multiple functional groups that are compatible andwilling to react with the functional groups in the base polymer or thefunctionalized extender. The gel may further comprise at least oneadditive selected from the group consisting of: flame retardants,coloring agents, adhesion promoters, stabilizers, fillers, dispersants,flow improvers, plasticizers, slip agents, toughening agents, andcombinations thereof.

In some embodiments, the gel comprises between 0.1 wt % and 5 wt % of astabilizer. The stabilizer may be selected from the group consisting ofantioxidants, acid-scavengers, light and UV absorbers/stabilizers, heatstabilizers, metal deactivators, free radical scavengers, carbon black,antifungal agents, and mixtures thereof.

In certain embodiments, the crosslinker is a covalent crosslinkerselected from the group consisting of primary amines, secondary amines,tertiary amines, epoxies, hydroxyl-terminated butadienes, polymericdi-isocynates, and mixtures thereof. In one embodiment, the crosslinkeris an ionic crosslinker. The ionic crosslinker may be a metal saltselected from the group consisting of aluminum acetylacetonate, ironacetylacetonate, zinc acetylacetonate, titanium acetylacetonate andzirconium acetylacetonate, aluminum triacetate, aluminium diacetate,aluminium monoacetate, tetra(2-ethylhexyl)titanate, and mixturesthereof. In some embodiments, the crosslinker is an amine crosslinkerselected from the group consisting of ethylene diamine; 1,2- and1,3-propylene diamine; 1,4-diaminobutane; 2,2-dimethylpropanediamine-(1,3); 1,6-diaminohexane; 2,5-dimethylhexane diamine-(2,5);2,2,4-trimethylhexane diamine-(1,6); 1,8-diaminooctane;1,10-diaminodecane; 1,11-undecane diamine; 1,12-dodecane diamine;1-methyl-4-(aminoisopropyl)-cyclohexylamine-1;3-aminomethyl-3,5,5-trimethyl-cyclohexylamine-(1);1,2-bis-(aminomethyl)-cyclobutane; p-xylylene diamine; 1,2- and1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin;1-methyl-4-aminoisopropyl-cyclohexylamine-1; 4,4′-diamino-dicyclohexyl;4,4′-diamino-dicyclohexyl methane;2,2′-(bis-4-amino-cyclohexyl)-propane;3,3′-dimethyl-4,4′-diamino-dicyclohexyl methane;1,2-bis-(4-aminocyclohexyl)-ethane;3,3′,5,540-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane;1,4-bis-(2-aminoethyl)-benzene; benzidine; 4,4′-thiodianiline,dianisidine; 2,4-toluenediamine, diaminoditolylsulfone;2,6-diaminopyridine; 4-methoxy-6-methyl-m-phenylenediamine;diaminodiphenyl ether; 4,4′-bis(o-toluidine); o-phenylenediamine;o-phenylenediamine, methylenebis(o-chloroaniline);bis(3,4-diaminiophenyl)sulfone; diaminiodiphenylsulfone;4-chloro-o-phenylenediamine; m-aminobenzylamine; m-phenylenediamine;4,4′-methylenedianiline; aniline-formaldehyde resin; trimethylene glycoldi-p-aminobenzoate; bis-(2-aminoethyl)-amine; bis-(3-aminopropyl)-amine;bis-(4-aminobutyl)-amine; bis-(6-aminohexyl)-amine; isomeric mixtures ofdipropylene triamine and dibutylene triamine; and mixtures thereof.

In other embodiments, the crosslinker is a polyol crosslinker selectedfrom the group consisting of 1,2-propanediol, 1,3-propanediol,diethanolamine, triethanolamine,N,N,N,N′-[tetrakis(2-hydroxyethyl)ethylene diamine], N,N,-diethanolaniline, polycaprolactone diol, poly(propylene glycol),poly(ethylene glycol), poly(tetramethylene glycol), and polybutadienediol and their derivatives or copolymers, and mixtures thereof.

In certain embodiments, the base polymer comprises a styrenic blockcopolymer. The styrenic block copolymer may be astyrene-ethylene/butylene-styrene, styrene-ethylene/propylene-styrenecopolymer or styrene butadiene styrene. In other embodiments, the basepolymer comprises a maleated base polymer.

In certain embodiments, the functionalized extender comprises a singleolefin at a terminal position on the extender. The functionalizedextender may be a polyisobutylene. The functionalized extender may alsobe a maleated extender, such as a maleated polyisobutylene.

In certain embodiments, the gel comprises one or more of the followingproperties: (a) hardness between 80 g and 300 g; (b) a stress relaxationbetween 20% and 65% when the gel is subjected to a deformation of 50% ofits original size; (c) a compression set between 4% and 20% after 50%strain has applied to the gel for 1000 hours at 70° C.; and (d) lessthan 10% oil bleed out after being under compression of 1.2 atm for 60days at 60° C.

In another embodiment, a closure or interconnect system is providedcomprising a housing, a cable, and a hybrid thermoplastic gel. Theclosure or interconnect system is made by reacting a functionalizedextender, and a base polymer having at least one functional groupcapable of crosslinking.

In some embodiments, the gel in the system further comprises acrosslinker having multiple functional groups that are compatible andwilling to react with the functional groups in the base polymer orfunctionalized extender. The gel may be compatible with a LSZH cable asdetermined by a pressure loss test or tightness test following at leastone of the following mechanical or environmental tests: axial tensiontest, flexure test, re-entry test, torsion test, resistance toaggressive media test, resistance to stress cracking test, salt fogtest, temperature cycling test, and waterhead test. In some embodiments,the gel in the system has less than 10% oil bleed out after being undercompression of 1.2 atm for 60 days at 60° C. In other embodiments, thegel in the system has less than 5% oil bleed out after being undercompression of 1.2 atm for 60 days at 60° C. In yet other embodiments,the closure or interconnect system further comprises a connector and areceptacle for the connector.

In an additional embodiment, a telecommunications apparatus is providedcomprising a telecommunications component. The apparatus furthercomprises a sealant that forms a seal with the telecommunicationscomponent, the sealant having a first range of elongation followed by asecond range of elongation, the sealant having a stress-strain profilehaving a first stress-strain slope corresponding to the first range ofelongation and a second stress-strain slope corresponding to the secondrange of elongation, the second stress-strain slope being steeper thanthe first stress-strain slope. In certain embodiments, a transition areaor slope exists between the first stress-strain slope and the secondstress-strain slope. In certain embodiments, the telecommunicationscomponent is a cable. In some embodiments, the telecommunicationscomponent comprises a housing.

In another embodiment, a sealant is provided comprising a sealantmaterial having a first range of elongation followed by a second rangeof elongation, the sealant material having a stress-strain profilehaving a first stress-strain slope corresponding to the first range ofelongation and a second stress-strain slope corresponding to the secondrange of elongation, the second stress-strain slope being steeper thanthe first stress-strain slope. As previously noted, a transition area orslope may exist between the first stress-strain slope and the secondstress-strain slope.

In yet another embodiment, an enclosure is provided comprising a housingdefining an opening. The enclosure further comprises a sealantarrangement positioned within the opening of the housing, the sealantarrangement defining at least one cable port, the sealant arrangementincluding a sealant material having a first range of elongation followedby a second range of elongation, the sealant material having astress-strain profile having a first stress-strain slope correspondingto the first range of elongation and a second stress-strain slopecorresponding to the second range of elongation, the secondstress-strain slope being steeper than the first stress-strain slope.The enclosure further comprises an actuation arrangement forpressurizing the sealant material within the opening of the housing. Incertain embodiments, the actuation arrangement includes a spring forpressurizing the sealant material.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a depiction of an interconnect system having a connection hubhaving multiple connection ports or receptacles for the connector,housing, and cable components to be connected.

FIG. 2 is a depiction of a connector, housing, and cable assembly withradial sealing.

FIG. 3 is a depiction of a connector, housing, and cable assembly withaxial sealing.

FIGS. 4 a and 4 b are depictions of a straight two piece housingassembly designed for axial sealing.

FIGS. 5 a and 5 b are depictions of an angled two piece housing assemblydesigned for axial sealing.

FIG. 6 is a side view of a telecommunications enclosure suitable forusing a sealant in accordance with the principles of the presentdisclosure.

FIG. 7 is an end view of the telecommunications enclosure of FIG. 6.

FIG. 8 is an exploded view of the telecommunications enclosure of FIG.6.

FIG. 9 is a cross-sectional view taken along section line 9-9 of FIG. 7.

FIG. 10 is a cross-sectional view taken along section line 10-10 of FIG.6.

FIG. 11 is a chart illustrating extender bleed out as a function of timefor two compositions under the conditions of heat (70° C.) and pressure(50 kPa or 0.5 atm).

FIG. 12 is a chart illustrating the stress-strain differences betweenconventional and hybrid gels.

DETAILED DESCRIPTION

As used herein, terms such as “typically” are not intended to limit thescope of the claimed invention or to imply that certain features arecritical, essential, or even important to the structure or function ofthe claimed invention. Rather, these terms are merely intended tohighlight alternative or additional features that may or may not beutilized in a particular embodiment of the present invention.

As used herein, the terms “comprise(s),” “include(s),” “having,” “has,”“contain(s),” and variants thereof, are intended to be open-endedtransitional phrases, terms, or words that do not preclude thepossibility of additional acts or structure.

As used herein, the term “polymer” may refer to a polymeric compoundprepared by polymerizing monomers, whether of the same or a differenttype. The generic term “polymer” embraces the terms “homopolymer,”“copolymer,” and the like.

As used herein, the term “functionalized extender” may refer to anycompound having a functional group that is compatible and willing toreact with a functional group in the base polymer or thecrosslinker/coupling agent. In certain embodiments, the term refers toany compound comprising a single functional site that is capable offorming a connection to a base polymer or a crosslinker/coupling agent.In certain embodiments, the functionalized extender is a maleatedextender, such as maleated polyisobutylene.

Any concentration range, percentage range, or ratio range recited hereinare to be understood to include concentrations, percentages, or ratiosof any integer within that range and fractions thereof, such as onetenth and one hundredth of an integer, unless otherwise indicated. Also,any number range recited herein relating to any physical feature are tobe understood to include any integer within the recited range, unlessotherwise indicated. It should be understood that the terms “a” and “an”as used above and elsewhere herein refer to “one or more” of theenumerated components. For example, “a” polymer refers to one polymer ora mixture comprising two or more polymers.

In certain embodiments, the hybrid thermoplastic gel is made through themixture and reaction of a base polymer with a functionalized extender inthe presence of heat (i.e., wherein the reaction is conducted at anelevated temperature greater than 25° C.). In some embodiments, the gelfurther comprises a crosslinker, wherein the gel is made through thereaction of a base polymer, functionalized extender, and crosslinker inthe presence of heat.

Making the Hybrid Thermoplastic Gel

In certain embodiments, the hybrid thermoplastic gel is prepared bymixing between 5-40 wt % base polymer, 60-95 wt % functional extender,and 0-10 wt % crosslinker (or coupling agent). In another embodiment,the gel is prepared by mixing 10-30 wt % base polymer, 70-90 wt %functional extender, and 0.1-5 wt % crosslinker. In yet anotherembodiment, the gel is prepared by mixing 15-25 wt % base polymer, 75-85wt % functional extender, and 0.5-3.5 wt % crosslinker.

In certain embodiments, the gel components are mixed together at anelevated temperature (i.e., greater than room temperature) for a certainperiod of time. The temperature and time at temperature may be adjustedaccordingly to target the end properties desired in the gel. Several ofthose properties are discussed in the section below labeled “Uses andProperties of the Hybrid Thermoplastic Gel.” In certain embodiments, themixing and reacting is conducted at an elevated temperature between100-250° C., 150-220° C., or 180-200° C. In some embodiments, the mixingat the elevated temperature is held for 1-12 hours, 2-8 hours, or 3-6hours.

In certain embodiments, no catalyst or initiator is needed other thanheat to react the base polymer, functionalized extender, and/orcrosslinker together to form the hybrid thermoplastic gel. For example,certain ionic crosslinkers (described below in greater detail) may onlyneed heat and time to react and form the gel.

In certain embodiments, an additive or additives may also be added tothe gel composition. In certain embodiments, the additive may comprisebetween 0.1-30 wt % of the overall composition, 1-25 wt % of the overallgel composition, or 5-20 wt % of the overall composition. In particular,the gel may include a stabilizer comprising between 0.1-5 wt %, 0.5-3 wt%, or 1-2 wt % of the overall gel composition.

In some embodiments, the base polymer and/or functionalized extender aremaleated prior to the mixing discussed above. The maleated reaction ofthe base polymer and/or functionalized extender is discussed in greaterdetail below.

Base Polymer

In certain embodiments, the base polymer comprises at least onefunctional group configured to chemically crosslink in the presence ofan extender or crosslinker. For example, the base polymer may havefunctional groups such as acyls, hydroxyls, sulfhydryls, amines,carboxyls, anhydrides, olefins, and carboxylic acids configured tochemically link in the presence of an extender or crosslinker.

In some embodiments, the base polymer is a styrenic block copolymer. Incertain embodiments, the styrenic block copolymer is astyrene-ethylene/butylene-styrene (“SEBS”),styrene-ethylene/propylene-styrene (“SEPS”) copolymer or styrenebutadiene styrene (SBS). In yet other embodiments, the base polymer is aolefinic block copolymer, such as those described in U.S. PatentApplication No. 2012/0130011, herein incorporated by reference in itsentirety. For example, the olefinic block copolymers may be anelastomeric copolymers of polyethylene, sold under the trade name INFUSEby The Dow Chemical Company of Midland, Mich. (e.g., INFUSE 9107). Inone embodiment, the olefinic block copolymer is selected from the groupconsisting of INFUSE OBC 9000, INFUSE OBC 9007, INFUSE OBC 9100, INFUSEOBC 9107, INFUSE OBC 9500, INFUSE OBC 9507, INFUSE OBC 9530, INFUSE OBC9807, INFUSE OBC 9817, and mixtures thereof.

In other particular examples, the base polymer may be any suchconfigured polymers such as those available from Kraton Polymers(Houston, Tex.), including but not limited to: Kraton MD6684, RP6684,FG190, FG1924, RP6670, 1901, 1901X, B 51-4, FG 120LX, FG 1652, FG 19, FG1900X, FG 1901, FG 1901X, FG 1901X951, FG 1921X, FG 1924, FG 1924X, FG1961X, G 1901, G 1901X, G 1901X2, G 1921, GRP 6627, KG 1901, M 1923, MB1000, RP 6509, RP 6510, RP 6543, RP 6562. In other embodiments, the basepolymer may be at least one of the following available from Asahi KaseiElastomer (Tokyo, Japan): Asahi M 1913, M 1943, and M 1953.

In other embodiments, the base polymer may further include at least oneof the following commercially available copolymers, includinghydrogenated styrenic block copolymers such as thepolystyrene-poly(ethylene-propylene) diblock copolymers available fromKraton Polymers as KRATON G1701 and G1702; thepolystyrene-poly(ethylene-butylene)-polystyrene triblock copolymersavailable from Kraton Polymers as KRATON G1641, G1650, G1651, G1654,G1657, G1726, G4609, G4610, GRP-6598, RP-6924, MD-6932M, MD-6933, andMD-6939; the polystyrene-poly(ethylene-butylene-styrene)-polystyrene(S-EB/S-S) triblock copolymers available from Kraton Polymers as KRATONRP-6935 and RP-6936, thepolystyrene-poly(ethylene-propylene)-polystyrene triblock copolymersavailable from Kraton Polymers as KRATON G1730; thepolystyrene-poly(ethylene-butylene)-polystyrene triblock copolymercomprising 67 wt % polystyrene available from Asahi Kasei Elastomer asTUFTEC H1043; the polystyrene-poly(ethylene-butylene)-polystyrenetriblock copolymer comprising 42 weight percent polystyrene availablefrom Asahi Kasei Elastomer as TUFTEC H1051; thepolystyrene-poly(butadiene-butylene)-polystyrene triblock copolymersavailable from Asahi Kasei Elastomer as TUFTEC P1000 and 2000; thepolystyrene-polybutadiene-poly(styrene-butadiene)-polybutadiene blockcopolymer available from Asahi Kasei Elastomer as S.O.E.-SS L601; thepolystyrene-poly(ethylene-butylene)-polystyrene triblock copolymercomprising about 60 wt % polystyrene available from Kuraray as SEPTONS8104; the polystyrene-poly(ethylene-ethylene/propylene)-polystyrenetriblock copolymers available from Kuraray as SEPTON® S4044, S4055,S4077, and S4099; and thepolystyrene-poly(ethylene-propylene)-polystyrene triblock copolymercomprising about 65 wt % polystyrene available from Kuraray as SEPTON®S2104. Mixtures of two or more block copolymers may be used.Illustrative commercially available unhydrogenated block copolymersinclude the Kraton D series polymers, including KRATON D1101 and D1102,from Kraton Polymers, and the styrene-butadiene radial teleblockcopolymers available as, for example, K-RESIN KR01, KR03, KR05, and KR10sold by Chevron Phillips Chemical Company. In another embodiment, thestyrenic block copolymer is a mixture of high melt viscosity SEBS blockcopolymer and a functionalized SEBS block copolymer.

In another embodiment, the base polymer comprises maleic anhydridegrafted to the block copolymer. The maleated functional groups areexamples of functional groups configured for crosslinking during gelprocessing. These maleated base polymers are particularly configured forcrosslinking with extenders, di- and multi-amine crosslinkers, di- andmulti-functional epoxies, di- and multi-functional hydroxyl molecules(alcohols and polyols) as well as aluminum, titanium and otherorganometallic compounds. In some embodiments, the maleated base polymerincludes at least one functional group configured to chemicallycrosslink with a di- and multi-amine crosslinker.

For further example, the maleated functional groups of a maleicanhydride-modified SEBS or SEPS are configured for crosslinking. Notwishing to bound by theory, but it is believed that chemicalcrosslinking of the SEBS or SEPS triblocks at the ethylene-butylene orethylene-propylene blocks further strengthens the gel structure. Thechemical crosslinking produced is capable of raising its softeningtemperature.

Methods of preparing maleated block copolymers are known in the art andmany such block copolymers are commercially available. For example,maleated block copolymers are disclosed in EP 0879832A1. Illustrativecommercially available maleic anhydride-modified SEBS are available fromKraton Polymers (Houston, Tex.) as KRATON FG1901 (SEBS polymer having apolystyrene content of about 30 wt % and maleic anhydride graftedcontent of about 1.4-2.0 wt %) and KRATON FG 1924 G (SEBS polymer withabout 13 wt % polystyrene and maleic anhydride grafted content of about0.7-1.3 wt %), and KRATON MD 6684 CS (SEBS polymer having a polystyrenecontent of about 30 wt % and maleation level of about 1.0 wt %), andKRATON MD 6670. Illustrative commercially available maleicanhydride-modified SEBS are available from Asahi Chemical Industry Co.,Ltd. (Tokyo, Japan) under the trade name M-1911 (maleation level ofabout 3.0 wt %), M-1913 (maleation level of about 2.0 wt %), and M-1943.

In one embodiment, the maleic anhydride modified SEBS is KRATONMD6684CS. In another embodiment, the maleic anhydride-modified SEBS isKRATON FG6684. In yet another embodiment, the maleic anhydride modifiedSEBS is selected from the group consisting of as KRATON FG1901, KRATONFG 1924 G, KRATON MD 6684 CS, and KRATON MD 6670. In another embodiment,the maleic anhydride-modified SEBS has a maleation level of between 1.0wt % and 3.0 wt %.

Functionalized Extender

In certain embodiments, the hybrid thermoplastic gel includes afunctionalized extender that is capable of forming a connection with thebase polymer and “extend” the length of the base polymer. In certainembodiments, the functionalized extender comprises at least onefunctional group that is compatible and willing to react with afunctional group in the base polymer or the crosslinker/coupling agent.In certain embodiments, the functionalized extender may be any compoundthat comprises a functional site that is capable of forming a connectionto the base polymer or the crosslinker/coupling agent. The functionalgroup may be an olefin, for example.

In some embodiments, the functionalized extender comprises an internalolefin. In other embodiments, the functionalized extender comprises aterminal double bond (α-olefin). In certain embodiments, thefunctionalized extender includes only one functional group. In someembodiments, the functionalized extender comprises a single, terminalolefin. Not wishing to bound by theory, but it is believed that when thefunctionalized extender includes only one functional group per molecule(such as a terminal double bond), then a highly crosslinked structurecan be prevented by the stoichiometry of the components, and theresulting gel can be melt processed more readily. A functionalizedextender containing only one functional group can assist in locking theextender into the gel structure and prevent the extender from bleedingout as readily as similar gels made with non-functionalized(non-reactive) extenders.

In other embodiments, the functionalized extender comprises more thanone functional group. The functionalized extender may comprise acompound having more than one olefinic site such as a butadiene. In oneparticular embodiment, the functionalized extender comprises acarboxy-terminated butadiene compound.

In certain embodiments, the extender can be locked into the gelstructure either by making it physically or chemically attracted to thepolymeric or functional portion of the base polymer, or by adding acrosslinker (or coupling agent) that connects the functionalizedextender to the base polymer. In a preferred embodiment, thefunctionalized extender is connected to the base polymer (eitherdirectly or through a coupling agent) in only one location per extendermolecule.

In some embodiments, the functionalized extender is selected from thegroup consisting of: polyisobutylene, unsaturated hydrocarbon oils,unsaturated paraffins, alkenes or olefins, unsaturated naturals oilssuch as castor, linseed, soybean, peanut, esters or phthalate esters,polybutadiene, polyisoprene, poly(butadiene/styrene) copolymers, otherliquid rubbers, and mixtures thereof. In one embodiment, thefunctionalized extender is polyisobutylene.

In certain embodiments, the functionalized extender is a maleatedextender, such as maleated polyisobutylene or maleated polybutadiene. Inone particular embodiment, the functionalized extender is maleatedpolyisobutylene. In some embodiments, the extender compound is reactedwith maleic anhydride to form a maleated extender. In one particularexample, about 45 g of maleic anhydride is added to about 500 g ofheated polyisobutylene (TPC 595 from Texas Petrochemicals, Houston,Tex.), wherein the reaction is carried out at 190° C. for 6 hours. Thehot maleated polyisobutylene is then filtered through a 200 mesh filterto remove any charred particles, and then put in sealed glass containersunder dry nitrogen. The resulting composition was approximately 80%maleated as determined by the stoichiometry of the ingredients andaverage molecular weight of the polyisobutylene. Other functionalizedextenders (including other polyisobutylene compositions such as Indopol®H100 polyisobutylene, INEOS Oligomers, League City, Tex., or Glissopal1300 from BASF) may also maleated using a similar procedure.

Crosslinker/Coupling Agent

In certain embodiments, the hybrid thermoplastic gel includes acrosslinker or coupling agent that is capable of forming connectionsbetween the base polymer chains, between the base polymer andfunctionalized extender, or between functionalized extenders. In certainembodiments, the crosslinker comprises multiple (2 or more) functionalgroups that are compatible and willing to react with the functionalgroups in the base polymer or functionalized extender. In certainembodiments, the crosslinker comprises between three and ten functionalgroups that are capable of forming a connection point between three andten base polymers or functionalized extenders, such that the crosslinkerfunctions as a branching agent. In another embodiment, the crosslinkercomprises four functional groups that are capable of forming aconnection point between four different base polymers or functionalizedextenders.

Any crosslinker capable of reacting with the functionalized base polymerregions can be utilized, such as covalent bond crosslinking (covalentcrosslinkers) or ionic bond crosslinking (ionic crosslinkers).

In certain embodiments, the crosslinker is an ionic crosslinker, whichmay allow for improved re-melting or re-processing the gel by breakingor disassociating the bond at an elevated temperature. In certainembodiments, an ionic crosslinked hybrid gel may be re-melted orre-processed by placing the gel sample in a picture frame mold (in somecases, a mold that is has dimensions of about 200 mm by 200 mm by 3 mmwith sheets of release paper or film on each side of the gel samples,wherein the total amount of gel placed in the mold is 60 g). Thematerial may then be pressed in a heated hydraulic press for 2-3 minutes(or until melted) at about 180° C. and 10000 pounds of force. The samplemay then be cooled to room temperature and removed. Samples of othershapes can be molded in a manner similar to injection molding plastic.In some embodiments, the re-melting/re-processing temperatures may rangebetween about 190° C. and 230° C., and the pressures may range betweenabout 300 psi and 1000 psi depending on the size and geometry of thesample. Plastic injection molding machines, pressurized drum melters,and gear pumps may all be used to melt gel and pressurize the gel toforce it into the desired mold.

In some embodiments, the ionic crosslinker is a metal salt. Organicmetal salts may aid in coupling the (maleated) extender to the basepolymer molecules. In certain embodiments, the metal salt is a lithium,sodium, calcium, aluminum, or zinc organic metal salts. In oneembodiment, the ionic crosslinker is a calcium salt (such as Licomont®CaV 102).

In one embodiment, the ionic crosslinker is aluminum acetylacetonate. Infurther embodiments, the ionic crosslinker is selected from the groupconsisting of aluminum acetylacetonate, iron acetylacetonate, zincacetylacetonate, titanium acetylacetonate and zirconium acetylacetonate,and mixtures thereof. In one embodiment, the crosslinker is an aluminumsalt of acetic acid. For example, the crosslinker may be an aluminumtriacetate (Al(C₂H₃O₂)₃), aluminium diacetate, (HO(Al(C₂H₃O₂)₃), oraluminium monoacetate, ((HO)₂(Al(C₂H₃O₂)₃). In another embodiment, thecrosslinker is tetra(2-ethylhexyl)titanate.

In certain embodiments, the chemical crosslinking involves covalentcrosslinking (or a covalent crosslinker). Non-limiting examples ofcovalent crosslinkers include primary, secondary, or tertiary amines,epoxies, hydroxyl-terminated butadienes, polymeric di-isocynates, andmixtures thereof.

In other embodiments, the covalent crosslinker is an amine crosslinker.In further embodiments, the amine crosslinker is selected from the groupconsisting of an organic amine, an organic diamine, and an organicpolyamine. In other embodiments, the amine crosslinker is selected fromthe group consisting of ethylene diamine; 1,2- and 1,3-propylenediamine; 1,4-diaminobutane; 2,2-dimethylpropane diamine-(1,3);1,6-diaminohexane; 2,5-dimethylhexane diamine-(2,5);2,2,4-trimethylhexane diamine-(1,6); 1,8-diaminooctane;1,10-diaminodecane; 1,11-undecane diamine; 1,12-dodecane diamine;1-methyl-4-(aminoisopropyl)-cyclohexylamine-1;3-aminomethyl-3,5,5-trimethyl-cyclohexylamine-(1);1,2-bis-(aminomethyl)-cyclobutane; p-xylylene diamine; 1,2- and1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin;1-methyl-4-aminoisopropyl-cyclohexylamine-1; 4,4′-diamino-dicyclohexyl;4,4′-diamino-dicyclohexyl methane;2,2′-(bis-4-amino-cyclohexyl)-propane;3,3′-dimethyl-4,4′-diamino-dicyclohexyl methane;1,2-bis-(4-aminocyclohexyl)-ethane;3,3′,5,5′-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane;1,4-bis-(2-aminoethyl)-benzene; benzidine; 4,4′-thiodianiline,dianisidine; 2,4-toluenediamine, diaminoditolylsulfone;2,6-diaminopyridine; 4-methoxy-6-methyl-m-phenylenediamine;diaminodiphenyl ether; 4,4′-bis(o-toluidine); o-phenylenediamine;o-phenylenediamine, methylenebis(o-chloroaniline);bis(3,4-diaminiophenyl)sulfone; diaminiodiphenylsulfone;4-chloro-o-phenylenediamine; m-aminobenzylamine; m-phenylenediamine;4,440 -C1-C6-dianiline such as 4,4′-methylenedianiline;aniline-formaldehyde resin; and trimethylene glycol di-p-aminobenzoateand mixtures thereof.

In further embodiments, the amine crosslinker is selected from the groupconsisting of bis-(2-aminoethyl)-amine, bis-(3-aminopropyl)-amine,bis-(4-aminobutyl)-amine and bis-(6-aminohexyl)-amine, and isomericmixtures of dipropylene triamine and dibutylene triamine. In yet furtherembodiments, the amine crosslinker is selected from the group consistingof hexamethylene diamine, tetramethylene diamine, and dodecane diamineand mixtures thereof.

In other embodiments, the covalent crosslinker is a polyol crosslinker.In further embodiments, the polyol crosslinker is selected from thegroup consisting of polyether-polyols, polyester-polyols, branchedderivatives of polyether-polyols (derived from, e.g., glycerine,sorbitol, xylitol, mannitol, glucosides, 1,3,5-trihydroxybenzene),branched derivatives of polyether-polyols (derived from, e.g.,glycerine, sorbitol, xylitol, mannitol, glucosides,1,3,5-trihydroxybenzene), orthophthalate-based polyols, ethyleneglycol-based polyols, diethylene glycol-based aromatic and aliphaticpolyester-polyols. In further embodiments, the polyol crosslinker isselected from the group consisting of 1,2-propanediol, 1,3-propanediol,diethanolamine, triethanolamine,N,N,N,N′-[tetrakis(2-hydroxyethyl)ethylene diamine],N,N,-diethanolaniline. In other embodiments, the polyol crosslinker isselected from the group consisting of polycaprolactone diol,poly(propylene glycol), poly(ethylene glycol), poly(tetramethyleneglycol), and polybutadiene diol and their derivatives or copolymers.

Additives

In certain embodiments, the thermoplastic gel composition may compriseadditional components. For example, the gel composition may includeadditives such as flame retardants, coloring agents, adhesion promoters,antioxidants, stabilizers, fillers, dispersants, flow improvers,plasticizers, slip agents, toughening agents, and combinations thereof.

In certain embodiments, the gel composition comprises an antioxidant orstabilizer such as a hindered phenol (e.g., Irganox™ 1076, commerciallyavailable from Ciba-Geigy Corp., Tarrytown, N.Y.), phosphites (e.g.,Irgafos™ 168, commercially available from Ciba-Geigy Corp.), metaldeactivators (e.g., Irganox™ D1024, commercially available fromCiba-Geigy Corp.). and sulfides (e.g., Cyanox LTDP, commerciallyavailable from American Cyanamid Co., Wayne, N.J.), light stabilizers(e.g., Cyasorb UV-531, commercially available from American CyanamidCo.), and/or phosphorous containing organic compounds (e.g., Fyrol PCFand Phosflex 390, both commercially available from Akzo Nobel ChemicalsInc. of Dobbs Ferry, N.Y.) and acid scavengers (e.g., DHT-4A,commercially available from Kyowa Chemical Industry Co. Ltd throughMitsui & Co. of Cleveland, Ohio, and hydrotalcite). Other suitableadditives include colorants, biocides, tackifiers and the like describedin “Additives for Plastics, Edition 1” published by D.A.T.A., Inc. andThe International Plastics Selector, Inc., San Diego, Calif.

In certain embodiments, the gel composition comprises a toughening agentthat may improve the ability for the composition to deform withoutbreaking. In some embodiments, the toughening agent may allow thecomposition to be strained to approximately 800%, 1000%, or 1200% of itsoriginal size before breaking.

In certain embodiments, the toughening agent is a fumed silica. Incertain embodiments, the fumed silica comprises between 0.1-30 wt % ofthe overall composition, 1-25 wt % of the overall composition, or 5-20wt % of the overall composition. One non-limiting example of a fumedsilica that may be used in the gel composition is AEROSIL® R9200modified, hydrophobic fumed silica, available from Evonik Degussa Corp.(Parsippany, N.J., USA).

In certain embodiments, the additional additives may include at leastone material selected from the group consisting of Dynasylan 40, PDM1922, Songnox 1024, Kingnox 76, DHT-4A, Kingsorb, pigment, and mixturesthereof. In some embodiments, the additives comprise between 0.1 and 25wt % of the overall composition, between 0.1 and 5 wt % of the overallcomposition, between 0.1 and 2 wt % of the overall composition, orbetween 0.1 and 1 wt % of the overall composition.

In some embodiments, the compositions disclosed and by methods disclosedherein comprise a flame retardant. In certain embodiments, the flameretardant is zinc oxide. In other embodiments, the flame retardant is ahalogenated paraffin (e.g., Bromoklor 50, commercially available fromFerro Corp., Hammond, Ind.). In some embodiments, the flame retardantcomprises between 0.1 and 25 wt % of the overall composition, between0.1 and 5 wt % of the overall composition, between 0.1 and 2 wt % of theoverall composition, or between 0.1 and 1 wt % of the overallcomposition. In one embodiment, the flame retardant comprises 20 wt % ofthe overall gel composition.

In some embodiments, the compositions disclosed and made by methodsdisclosed herein contain at least one stabilizer. Stabilizers includeantioxidants, acid-scavengers, light and UV absorbers/stabilizers, heatstabilizers, metal deactivators, free radical scavengers, carbon black,and antifungal agents.

Uses and Properties of the Hybrid Thermoplastic Gel, and Testing Methods

The gels described herein may be used in a number of end uses due totheir improved properties, such as improved behavior in mechanicalstresses (e.g., vibration and shock) or ability to seal uneven orcomplicated structures (due to the ability to flow and adapt to the areaof the structure). In certain embodiments, the gel may be used in aninterconnect, cover, or closure system. In particular, the gel may beused in a fiber optic closure, electrical sealant, or electricalclosure. In some embodiments, the gels are used as gel wraps,clamshells, or gel caps. In further embodiments, the gels are used inthe inside of a residence. In other embodiments, the gels are usedoutside of a residence. Use of the gel within a closure or interconnectsystem may allow for a reduction in the number of components, framesize, or cost over other sealing mechanisms.

With regards to use as a sealant, the hybrid gels described herein tendto exhibit a unique stress-strain dynamic, as further described below.With an increase in strain beyond the point of the elastic (linear)portion of the curve, the gel exhibits a somewhat exponential increasein stress prior to the failure point. In other words, the gel tends tobecome even stiffer with an increase in strain or pressure on the gel asit approaches its failure point. In certain examples, such as within aclosure, the gel is stiff at the higher strain points near the ends ofthe closure, keeping the softer gel composition within the closure fromextruding out of the closure.

In certain embodiments, the gel is used as a dampener. In certainembodiments, the gel is used as a flame retardant sealant. In oneembodiment, the gel comprises a flame retardant additive (e.g., zincoxide) in order to function as a flame retardant sealant.

In certain embodiments, the gel is used in a closure or enclosuresystem. In certain embodiments, the closure system comprises a housing,a cable, and a gel. In some embodiments, the cable is a LSZH cable.

In some embodiment, the system further comprises a connector, and, insome instances, a receptacle or port, therein forming an interconnectsystem. The interconnect system may comprise a mini input/outputconnector, data connector, power connector, fiber optic connector, orcombination thereof. For example, the interconnect system may comprise aRJ-45 connector system. Non-limiting examples of interconnect systemsand components are displayed in FIGS. 1, 2, 3, 4 a, 4 b, 5 a, and 5 b.

The gel may be used to create a seal formed by displacement. In otherembodiments, the gel may be used to create a seal having radialfunctionality, axial functionality, or a combination thereof. In yetother embodiments, the gel may be used to create a seal formed bydisplacement and having radial and/or axial functionality.

FIGS. 1, 2, and 3 provide non-limiting examples of radial and axialfunctionality. FIG. 1 displays an example of a connection hub havingmultiple connection receptacles or ports for the cables 16 within thehousings 14 to be connected. FIG. 1 displays both radial connectionports 10 and axial connection ports 12. FIG. 2 displays a connector 26;housing 18, 28; and cable 16 assembly with radial sealing 22. FIG. 3displays a connector 26; housing 32, 34; and cable 16 assembly withaxial sealing 30, wherein the seal follows the surface of the axial port12 (as shown in FIG. 1). In certain embodiments, the housing may have aknob 20 that may be pushed inward to engage the latch 24 on theconnector 26, allowing the connector to be removed from the port.

In certain embodiments, the gel may be used to create a seal in ahousing assembly having multiple parts. For example, in one embodimentthe gel may be used in a straight two-piece housing assembly, as shownin FIGS. 4 a and 4 b. Similar to FIG. 3, FIGS. 4 a and 4 b display atwo-piece housing 32, 34, having axial sealing 30, wherein the sealfollows the surface of the axial port 12 (as shown in FIG. 1). Incertain embodiments, the housing may have a knob 20 that may be pushedinward to engage the latch 24 (as shown in FIG. 3) on the connector 26(as shown in FIG. 3), allowing the connector to be removed from theport.

In another embodiment, the gel may be used in an angled two-piecehousing assembly, as shown in FIGS. 5 a and 5 b. FIGS. 5 a and 5 bdisplay a connector 26; angled two-piece housing 36, 38; and cable 16assembly with axial sealing 30, wherein the seal follows the surface ofthe axial port 12 (as shown in FIG. 1). In certain embodiments, thehousing may have a knob 20 that may be pushed inward to engage the latch24 on the connector 26, allowing the connector to be removed from theport.

The gel may be sealed around the cable 16 by sliding a smaller diametergel formation over the cable to create a seal through interference. Inother embodiments, the seal may be created by molding the gel around theinside of the housing components and then snapping the housing, gel, andcable into place.

In some embodiments, the gel is used in a closure or interconnect systemthat is “compatible” with a low smoke zero halogen (LSZH) cable. Incertain embodiments, compatibility is measured by subjecting the sampleto one or more mechanical or environmental tests to test for certainfunctional requirements. In some embodiments, compatibility is measuredby passing a pressure loss test, tightness test, and/or visualappearance test. In certain embodiments, the gel in the closure orinterconnect system is compatible where a traditional thermoplasticelastomer gel would fail.

In certain embodiments, the gel is used as a sealant in atelecommunications enclosure. Non-limiting examples oftelecommunications enclosures are shown in FIGS. 6-10.

FIGS. 6-8 show a telecommunications enclosure 120 suitable for using asealing material in accordance with the principles of the presentdisclosure. The enclosure 120 includes a housing 122 having an end 124defining a sealing unit opening 126. The sealing unit opening 126 isdefined by a base 127 of the enclosure 120. The base 127 has a hollowsleeve-like configuration. A dome-style cover 129 is secured to the base127 by a channel clamp 125. The enclosure 120 also includes a sealingunit 128 (see FIGS. 8-10) that fits within the sealing unit opening 126.The sealing unit 128 includes a sealant arrangement 132 (see FIGS. 9 and10) defining a plurality of cable ports 130. The sealant arrangement caninclude a material having stress-strain characteristics in accordancewith the principles of the present disclosure. In certain embodiments,the sealant arrangement can include a hybrid gel of the type disclosedherein. When pressurized, the sealant arrangement 132 is configured forproviding seals about structures (e.g., cables, plugs, etc.) routedthough the cable ports 130 and is also configured for providing aperipheral seal with the housing 122. The enclosure 120 further includesan actuation arrangement 131 (see FIG. 9) for pressurizing the sealantarrangement 132 within the sealing unit opening 126. In otherembodiments, the housing can be an enclosure (e.g., an aerial enclosure)having a pass-through configuration with sealing units located atopposite ends of the enclosure. In certain embodiments, a framesupporting optical components (e.g., optical splices, optical splitters,optical splice trays, optical splitter trays, fiber management trays,passive optical splitters, wavelength division multi-plexers, etc.) canbe mounted within the enclosure 120.

Referring to FIG. 9, the actuation arrangement 131 includes inner andouter pressurization structures 160, 162 (e.g., plates, members, bodies,etc.). The sealant arrangement 132 is positioned between the inner andouter pressurization structures 160, 162. The actuation arrangement 131also includes a threaded shaft 149 that extends between the inner andouter pressurization structures 160, 162 and a nut 151 that is threadedon the threaded shaft 149. The actuation arrangement further includes aspring 152 for transferring a seal pressurization force to the sealantarrangement 132. The spring 152 is captured between the nut 151 and theouter pressurization structure 162. An extension 153 (e.g., a wrench orother tool) is used to turn the nut 151 a first rotational direction(e.g., clockwise) on the threaded shaft 149 causing the spring 152 to becompressed between the nut 151 and the outer pressurization structure.As the spring 152 is compressed, the threaded shaft 149 is tensioned andthe inner and outer pressurization structures 160, 162 are drawntogether. As the inner and outer pressurizations structures 160, 162 aredrawn together, the sealant arrangement 132 is pressurized between thepressurization structures 160, 162 causing the sealant arrangement 132to flow/deform to fill voids within the sealing unit opening 126, toform the peripheral seal with the housing 122, and to form seals aroundany cables or inserts positioned within cable ports 130. Thus, when theactuation arrangement 131 is actuated, the first and secondpressurization plates 60, 62 are spring biased toward one another suchthat spring pressure is applied through the sealant arrangement 132 forpressurizing the sealant arrangement 132 to maintain effective sealingover an extended period of time. In other embodiments, differentactuation configurations can be used. The sealant arrangement 132 can bede-pressurized by turning the nut 151 a second rotational direction(e.g., counterclockwise) on the shaft 149 to decompress the spring 152.

Referring to FIGS. 9 and 10, two cables 180 are shown passing throughthe cable ports 130 while the remainder of the cable ports 130 are shownblocked with plugs. The cables 180 include outer jackets 182 containinga plurality of buffer tubes 184. A plurality of optical fibers 186 arecontained in each of the buffer tubes 184. The cables 180 also includecenter strength members 188 (e.g., fiberglass reinforced epoxy rods)that provide the cables with tensile and compressive reinforcement. Inother embodiments, reinforcing members in the form aramid yarns or otherreinforcing structures can be used. In certain embodiments, the cables180 can be LSZH cables and the outer jackets include EVA. Whenpressurized, the sealant arrangement 132 contacts the outer jackets 182and forms cable seals 190 around peripheries of the cable jackets 182.When pressurized, the sealant arrangement 132 also contacts an interiorof the base 127 to form a peripheral seal 192 with the base 127. Cableshaving alternative constructions (e.g., flat drop cables, cables withoutbuffer tubes, cables without center strength members, etc.) can also beused.

The sealant of the sealant arrangement 132 can be designed with customstress-strain profile suitable for a given application. In certainembodiments, the stress-strain profile includes a first stress-strainslope corresponding to an initial elongation range and a secondstress-strain slope corresponding to a subsequent elongation range. Incertain embodiments, a transition area or slope exists between the firststress-strain slope and the second stress-strain slope.

In certain embodiments, the initial elongation range is from 0 to atleast 200 percent elongation, or from 0 to at least 400 percentelongation, or from 0 to at least 600 percent elongation. In otherembodiments, the initial elongation range exists at less than 600percent elongation, or at less than 400 percent elongation, or at lessthan 200 percent elongation. The subsequent elongation range preferablystarts at or after the end of the initial elongation range. The secondstress-strain slope preferably is steeper than the first stress strainslope. In certain embodiments, the second stress-strain slope is atleast 10 percent steeper than the first stress-strain slope (i.e., thesecond stress-strain slope is at least 1.1 times as steep as the firststress-strain slope). In other embodiments, the second stress-strainslope is at least 25 percent steeper than the first stress-strain slope(i.e., the second stress-strain slope is at least 1.25 times as steep asthe first stress-strain slope). In still other embodiments, the secondstress-strain slope is at least 50 percent steeper than the firststress-strain slope (i.e., the second stress-strain slope is at least1.5 times as steep as the first stress-strain slope). In additionalembodiments, the second stress-strain slope is at least 100 percentsteeper than the first stress-strain slope (i.e., the secondstress-strain slope is at least 2 times as steep as the firststress-strain slope). The first stress-strain slope can be suitable forallowing the sealant arrangement to deform and flow to effectively fillvoids within the opening 126 of the base 127. The second stress-strainslope profile can be suitable for inhibiting the sealant arrangement 132from escaping containment between the inner and outer pressurizationstructures 160, 162 when fully pressurized.

The stress-strain properties of the gel may be tested by forming a roundring sample cut from a 3 mm thick sheet of gel using a defect free steeldie set. The inside diameter of the ring is approximately 18 mm and theoutside diameter is 27 mm. Mechanical property tests are performed usinga universal test machine (Instron type) at a strain rate of 500 mm/min.The ring is placed in the test machine by slipping it over cylindricalpins 7 mm in diameter separated by a distance of 33 mm. One of thecylindrical pins is held in a stationary fixture while the other pin isheld in a fixture attached to a load cell. The sample is orientedbetween the two pins such that it is directly under the load cell and issubject solely to a uniaxial tensile force (i.e., no side loading). Thering sample is then pulled at 500 mm/min until failure.

Tightness may be tested under International Electrotechnical Commission(IEC) Test 61300-2-38, Method A and TEC 60068-2-17, Test Qc. In certainembodiments, tightness is tested by immersing the specimen in a waterbath and using an internal pressure of 20−40 kPa (0.2-0.4 atm) for 15minutes. It is important that tightness is measured directly afterinstalling the closure at a temperature of −15° C. or 45° C. It is alsoimportant that all the air bubbles present on the outside of the closureare removed. If a continuous stream of air bubbles is observed, thismeans the specimen is not properly sealed and it will be considered as afailure (i.e., not compatible).

Pressure loss may be tested under IEC 61300-2-38, Method B. In certainembodiments, the gel and cable are compatible if the difference inpressure before and after the test is less than 2 kPa (0.02 atm).

Visual appearance may be tested under IEC 61330-3-1 by examination ofthe product with the naked eye for defects that could adversely affectthe product performance.

The sample may be subjected to various mechanical and/or environmentalconditions prior to testing tightness, pressure loss, visual appearance,etc. In certain embodiments, compatibility is determined by subjectingthe sample to one or more of the following mechanical tests: axialtension test, flexure test, re-entry test, and torsion test, and/or oneor more environmental tests: resistance to aggressive media test,resistance to stress cracking test, salt fog test, temperature cyclingtest, and waterhead test.

In certain embodiments, the sample is subjected to an axial tension testaccording to IEC 61300-2-4. In this test, the sample may be pressuredinternally at 20 kPa (0.2 atm) or 40 kPa (0.4 atm) at room temperatureand sealed. The base assembly is clamped and a force is applied to eachof the extending cables individually. If the sample has an outerdiameter of less than or equal to 7 mm, then the amount of force percable applied is equal to (outer diameter/45 mm)*500 Newtons (“N”). Thisforce is applied for 15 minutes for each cable and built up to the IEC61300-2-4 test. If the sample has an outer diameter of greater than 7mm, then the amount of force per cable applied is equal to (outerdiameter/45 mm)*1000 N, with a maximum of 1000 N applied. This force isapplied for one hour. Internal pressure is then examined for pressureloss. In certain embodiments, the gel and cable are compatible if thepressure loss is less than 2 kPa (0.02 atm). In addition, in certainembodiments, the gel and cable are compatible if the displacement of thecable is less than 3 mm. In other embodiments, the specimens are furthersubjected to the tightness test, previously described.

In other embodiments, compatibility is measured by subjecting the sampleto a flexure test according to IEC 61300-2-37. In this test, the samplesare subjected to temperatures of −15° C. and 45° C. Samples arepressured internally at 20 kPa or 40 kPa (0.2 atm or 0.4 atm) andsealed. Cables are bent individually at an angle of 30° (or a maximumforce application of 500 N) each side of neutral in the same plane. Eachbending operation is held for 5 minutes. The cable is returned to itsoriginal position and then the procedure is repeated in the oppositedirection. After 5 cycles on each cable, the samples are visuallyinspected by the naked eye for appearance, conditioned at roomtemperature, and subjected to a tightness test. In some embodiments, thegel and LSZH cable are compatible if the specimen passes the visualappearance test, pressure loss test (i.e., less than 2 kPa (0.02 atm)),and/or tightness test.

In another embodiment, compatibility is measured by subjecting thesample to a re-entry test according to IEC 61300-2-33. In certainembodiments, re-entry can be simulated after a certain time oftemperature cycling. To complete this test, the closure has to beremoved from the cycling room and tested on tightness. After this areentry test can be done. In this test, a dummy plug or cable is removedfrom the closure and another cable or dummy plug is added. Then,tightness is measured again. Re-entry is successful if the closurepasses the tightness test again.

Another mechanical test may be employed to determine compatibility. Thesample may be subjected to a torsion test according to IEC 61300-2-5.After completion of the torsion test, the gel and cable may beconsidered compatible if the sample passes the visual inspection test,pressure loss test, and/or tightness test.

In yet other embodiments, compatibility is measured by conducting anenvironmental test of temperature cycling or accelerated aging under TEC61300-2-22 and TEC 60068-2-14, Test Nb. In one embodiment, thetemperature cycling test is conducted on the cable jacket between thegel blocks by cycling the temperature between −40° C. and 70° C. for 10days at two cycles between the extreme temperatures per day. In someembodiments, the humidity is uncontrolled, the dwell time is four hoursand the transition time is two hours. In certain embodiments, the cablejacket is tested for maintenance of tensile strength, ultimateelongation, tightness, visual appearance, and/or re-entry. Also, incertain embodiments, after the temperature cycling test, tightness ofthe closures needs to be tested after being conditioned to roomtemperature for a minimum of 2 hours. Therefore, in certain embodiments,the gel and LSZH cable are compatible if the specimen passes thetightness test.

In another embodiment, compatibility is determined by subjecting thesample to a resistance to aggressive media test under IEC 61300-2-34,ISO 1998/I, and EN 590. The sample is considered compatible if itsubsequently passes the tightness and/or appearance test.

In yet another embodiment, compatibility is determined by subjecting thesample to a resistance to stress cracking test under IEC 61300-2-34. Thesample is considered compatible if it subsequently passes the tightnesstest and/or shows no visible signs of cracking.

In other embodiments, compatibility is determined by subjecting thesample to a salt fog test under IEC 61300-2-36 and IEC 60068-2-11, TestKa. The sample is considered compatible if it subsequently passes thetightness and/or appearance test.

In some embodiments, compatibility is determined by subjecting thesample to a waterhead test under IEC 61300-2-23, Method 2. The sample isconsidered compatible if there is no water ingress.

In certain embodiments, the gel has measurable properties. For example,in some embodiments, the gel has a hardness in the range of 24 to 53Shore 000 Hardness, or 80 to 300 g, as measured according to methodsknown in the art. In certain embodiments, the shore hardness gauge ismeasured according to ISO868 or ASTM D2240. In other embodiments,hardness can be measured on a texture analyzer. For example, a LFRATexture Analyzer-Brookfield may include a probe assembly fixed to amotor driven, bi-directional load cell. In such a system, the probe isdriven vertically into the sample at a pre-set speed and to a pre-setdepth. The hardness is the amount of force needed to push the probe intothe test sample. In other embodiments, the gel has a hardness in therange of 37 to 45 Shore 000, or 160 to 220 g. In yet other embodiments,the gel has a hardness in the range of 38 to 42 Shore 000, or 170 to 200g.

For further example, the gel may have certain properties after beingsubjected to compression set testing. A modified version of ASTM D395,method B provides one method of compression set testing to determine theability of elastomeric materials to maintain elastic properties afterprolonged compressive stress. The test measures the somewhat permanentdeformation of the specimen after it has been exposed to compressivestress for a set time period. Under compression testing, the thicknessof the original specimen is measured and then the specimen is thenplaced between spacers and in a compression device. The specimen may becompressed to 25% or 50% of its original height, using spacers toaccurately measure the compression. Within two hours of assembly, thecompression device is placed in an oven at a specified temperature foran extended periods of time. After removing the sample from the oven,the specimen is allowed to cool (e.g., for 30 minutes) before measuringthe final thickness. In certain embodiment, the compression set of thegel sample, as measured after 50% strain has been applied for 1000 hoursat 70° C., has a range between 4% and 20%. In other embodiments, thecompression set, as measured after 50% strain has been applied for 1000hours at 70° C., has a range between 10% and 14% when measured accordingto the modified version of ASTM D395, method B described above.

In some embodiments, the gel is compressed with a certain strain ordeformation (e.g., in certain embodiments, to 50% of its original size).This causes a certain stress in the material. The stress is now reducedbecause the material relaxes. In certain embodiments, the stressrelaxation of the gel has a possible range between 20 and 65% whensubjected to a tensile strain or deformation of about 50% of the gel'soriginal size, wherein the stress relaxation is measured after a oneminute hold time at 50% strain. In other embodiments, the stressrelaxation of the gel is between 30% and 50% when subjected to a tensilestrain of about 50%. A higher stress relaxation indicates that once agel is installed in a closure, the gel will require less stress in orderfor it to seal.

In certain embodiments, the gel composition has less than 10% bleed outover a period of time when the gel is under compression of 50 kPa (0.5atm) or 120 kPa (1.2 atm) at 60° C. The weight of the gel sample isrecorded before and after the pressure has been applied. In certainembodiments, oil bleed out is measured on a wire mesh, wherein the oilloss may exit the gel through the mesh. Typically, gel samples should be3 mm±0.5 mm thick and have a diameter of 14 mm±0.5 mm, and three samplesshould be tested from each gel. The gel sample is placed into acylindrical hole/tube resting on a fine and rough screen, which givesenough support to hold the gel but in the meantime allows the oil toseparate from the gel. Pressure is applied to the gel by placing aweight on top of a piston (which prevents the gel from creeping out ofthe hole. Typically, approximately 50 kPa (0.5 atm) or 120 kPa (1.2 atm)of pressure is placed on the gel sample. Then, the sample is placed inan oven at 60° C. After 24 hours, the sample is removed from the oven toclean the surface oil and weigh the gel. The sample is then returned tothe oven. Weight measurements are taken every 24 hours untilstabilization has occurred (e.g., when 5 weight measurements areconstant).

In some embodiments, the gel has less than 8%, 6%, 4%, or 2% oil bleedout over the period of time. In certain embodiments, the oil loss ismeasured at 200 hours, 400 hours, 600 hours, 800 hours, 1000 hours, 1200hours, or 1440 hours (60 days).

In certain embodiments, the gel has less oil bleed out in comparison toa thermoplastic gel over the same period of time at 50 kPa (0.5 atm) or120 kPa (1.2 atm) at 60° C. In some embodiments, the gel has less than20%, 30%, 40%, 50%, or 60% of the oil bleed out of a similar,traditional thermoplastic gel at 200 hours, 400 hours, 600 hours, 800hours, 1000 hours, 1200 hours, 1440 hours (60 days), 2000 hours, or 3000hours.

EXAMPLES

A variety of gels and extended elastomers were made using modifiedextenders.

Example 1

A thermoplastic gel was made using the following formula:

Component Weight Percent Maleated TPC 595 82.5 Kraton MD6684 11.0 KratonG1701M 4.0 Irganox 1076 1.0 Irganox B225 0.75 Aluminum acetylacetonate(AlAcAc) 0.75

The components were combined at 200° C. using a multi-shaft high shearmixer until a uniform material was obtained (approximately 3 hours ofmixing). The composition of matter is a reduction to practice of severalof the key ideas disclosed. Maleated TPC 595 represents one embodimentof a functionalized extender. In addition, the formula contains basepolymers—maleated Kraton MD6684 and Kraton G1701M. The AlAcAc functionsas a coupling agent or ionic crosslinker. Irganox 1076 and Irganox B225function as stabilizer compositions.

There are several possibilities for the coupling agent, these includecoupling the TPC 595 to itself, coupling the TPC 595 to the MD 6684 andcoupling one MD6684 molecule to another. All three possibilities serveto inhibit the bleed out of the extender molecule by making it longer(two or more associated extender molecules), causing it to becomeassociated with the Kraton base polymer, or forming a Kraton networkthat is more difficult for the extender to squeeze out of. The gelformed in this example was a thermoplastic material and could bemelt-processed at 180° C. in a hot press.

Example 2

A thermoplastic gel was made using the following formula:

Component Weight Percent Maleated TPC 595 75.5 Kraton MD6684 15.0 KratonG1701M 5.0 Irganox 1076 1.0 Zinc acetylacetonate (ZnAcAc) 1.0 Aluminumacetylacetonate (AlAcAc) 2.5

This gel was made in a similar manner to the previous example and hadmany of the same characteristics, including reduced extender bleed outcompared with a current gel or elastomer formulation which did notcontain the functionalized extender.

Example 3

A thermoplastic gel was made using the following formula:

Component Weight Percent Maleated TPC 595 79.0 Kraton MD6684 6.0 KratonG1651 5.5 Kraton G1701M 5.0 Irganox 1076 1.0 Licomont ® CaV 102 (calciumsalt of 2.5 montanic acid)

This gel was made in a similar manner to the previous examples andillustrates that a wide variety of reductions to practice are possibleusing the concepts outlined in the first paragraphs. These conceptsinclude mixing maleated and non maleated Kratons as well as using avariety of organic metal salts to aid in coupling the maleated extenderto the polymer molecules. Lithium, sodium, zinc, and other organic metalsalts will also function as coupling agents. A variety of functionalizedextenders will also work in similar formulations. These include, but arenot limited to, acid modified polybutadienes, functionalized lowmolecular weight olefin waxes, and acrylic oligomers.

Comparative Example 1

A thermoplastic gel was made using the following formula:

Component Weight Percent Kaydol (white mineral oil) 78.0 Kraton G1651H15.0 Kraton G1701M 5.0 Irganox 1076 1.0 Irganox 1010 1.0

The gel composition comprising a reactive extender (Example 2) wascompared with a conventional material made with a non-reactive extender(Comparative Example 1). FIG. 11 illustrates the bleed out of the twocompositions under the conditions of heat (70° C.) and pressure (50 kPaor 0.5 atm).

As shown in FIG. 11, at all times, the bleed out of extender for Example2 was approximately half or less the bleed out of the conventionalmaterial (non-reactive extender in Comparative Example 1). A smallamount of extender bleeds out in Example 2 because there was a smallpercentage of extender that was either non-reacted, or was not attachedusing the ionic crosslinking agent (AlAcAc).

The gel composition in Comparative Example 1 was also compared withExample 3 for stress-strain performance. FIG. 12 illustrates thestress-strain differences between conventional and hybrid gels, whereinthe hybrid gel has a more viscous and less elastic stress-strain curveup to approximately 600% elongation.

As shown in FIG. 12, with an increase in strain beyond the point of theelastic (linear) portion of the curve, the hybrid gel of Example 3exhibits a somewhat exponential increase in stress prior to the failurepoint. In other words, the gel tends to become even stiffer with anincrease in strain or pressure on the gel as it approaches its failurepoint.

The gels may be tested in a number of ways, such as: temperaturecycling, re-entry test, sealing under water pressure, cold and hotinstallations, and kerosene exposure. For temperature cyclingexperiments, closures including the gels are exposed to temperaturesbetween −30° C. and +60° C. for 10 days. Humidity is typically notcontrolled. The closures are cycled between the high and lowtemperatures two times a day for ten days. Samples are maintained at theextreme temperatures for four hours during each cycle.

For combined temperature cycling tests, the gels are installed in threeclosure systems. After installation, the closures are tested ontightness and put into temperature cycling. After eight days, a re-entrytest is performed, and after ten days, the closures are taken out ofcycling and tested on tightness and re-entry. Closures containing thetraditional thermoplastic gels are also tested.

For tightness testing, the closure is immersed in a water bath for 15minutes and an internal pressure of 20 kPa. If air bubbles are observed,this means the closure is not properly sealed and it will be consideredas a failure.

For re-entry testing, a dummy plug or cable is removed from the closureand another cable or dummy plug is added. Then, tightness is measuredagain. Re-entry is successful if the closure passes the tightness testagain.

In certain embodiments, the gel in the closure system may be able topass the tightness and re-entry tests where a traditional thermoplasticelastomer gel would fail.

Although examples have been described herein, it should be appreciatedthat any subsequent arrangement designed to achieve the same or similarpurpose may be substituted for the specific examples shown. Thisdisclosure is intended to cover any and all subsequent adaptations orvariations of various examples. Combinations of the above examples, andother examples not specifically described herein, may be apparent tothose of skill in the art upon reviewing the description.

The Abstract is provided with the understanding that it will not be usedto interpret or limit the scope or meaning of the claims. In addition,in the foregoing Detailed Description, various features may be groupedtogether or described in a single example for the purpose ofstreamlining the disclosure. This disclosure is not to be interpreted asreflecting an intention that the claimed examples require more featuresthan are expressly recited in each claim. Rather, as the followingclaims reflect, inventive subject matter may be directed to less thanall of the features of any of the disclosed examples. Thus, thefollowing claims are incorporated into the Detailed Description, witheach claim standing on its own as defining separately claimed subjectmatter.

The above disclosed subject matter is to be considered illustrative, andnot restrictive, and the appended claims are intended to cover all suchmodifications, enhancements, and other examples, which fall within thetrue spirit and scope of the description. Thus, to the maximum extentallowed by law, the scope is to be determined by the broadestpermissible interpretation of the following claims and theirequivalents, and shall not be restricted or limited by the foregoingdetailed description.

1. A method of making a hybrid thermoplastic gel comprising: providing abase polymer having at least one functional group capable ofcrosslinking; providing a functionalized extender; providing heat; andreacting the base polymer and functionalized extender in the presence ofthe heat to form the hybrid thermoplastic gel.
 2. The method of claim 1,further comprising providing a crosslinker having multiple functionalgroups that are compatible and willing to react with the functionalgroups in the base polymer or functionalized extender.
 3. The method ofclaim 1, further comprising providing at least one additive selectedfrom the group consisting of: flame retardants, coloring agents,adhesion promoters, stabilizers, fillers, dispersants, flow improvers,plasticizers, slip agents, toughening agents, and combinations thereof.4. The method of claim 1, further comprising providing between 0.1 wt %and 5 wt % of a stabilizer.
 5. The method of claim 4, wherein thestabilizer is selected from the group consisting of antioxidants,acid-scavengers, light and UV absorbers/stabilizers, heat stabilizers,metal deactivators, free radical scavengers, carbon black, antifungalagents, and mixtures thereof.
 6. The method of claim 1, wherein the basepolymer comprises a styrenic block copolymer.
 7. The method of claim 6,wherein the styrenic block copolymer is astyrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrenecopolymer.
 8. The method of claim 1, wherein the base polymer comprisesa maleated base polymer.
 9. The method of claim 1, wherein thefunctionalized extender comprises a single olefin at a terminal positionon the extender.
 10. The method of claim 1, wherein the functionalizedextender is a polyisobutylene.
 11. The method of claim 1, wherein thefunctionalized extender is a maleated extender.
 12. The method of claim11, wherein the maleated extender is a maleated polyisobutylene.
 13. Themethod of claim 1, wherein the gel comprises one or more of thefollowing properties: a) a hardness between 80 g and 300 g; b) a stressrelaxation between 20% and 65% when the gel is subjected to adeformation of 50% of its original size; c) a compression set between 4%and 20% after 50% strain has applied to the gel for 1000 hours at 70°C.; and d) less than 10% oil bleed out after being under compression of1.2 atm for 60 days at 60° C.
 14. A hybrid thermoplastic gel comprising:5-40 wt % of a base polymer having at least one functional group capableof crosslinking; 60-95 wt % of a functionalized extender; and 0-10 wt %of a crosslinker having multiple functional groups that are compatibleand willing to react with the functional groups in the base polymer orthe functionalized extender.
 15. The gel of claim 14 further comprisingat least one additive selected from the group consisting of: flameretardants, coloring agents, adhesion promoters, stabilizers, fillers,dispersants, flow improvers, plasticizers, slip agents, tougheningagents, and combinations thereof.
 16. The gel of claim 14, wherein thegel comprises between 0.1 wt % and 5 wt % of a stabilizer.
 17. The gelof claim 16, wherein the stabilizer is selected from the groupconsisting of antioxidants, acid-scavengers, light and UVabsorbers/stabilizers, heat stabilizers, metal deactivators, freeradical scavengers, carbon black, antifungal agents, and mixturesthereof.
 18. The gel of claim 14, wherein the crosslinker is a covalentcrosslinker selected from the group consisting of primary amines,secondary amines, tertiary amines, epoxies, hydroxyl-terminatedbutadienes, polymeric di-isocynates, and mixtures thereof.
 19. The gelof claim 14, wherein the crosslinker is an ionic crosslinker.
 20. Thegel of claim 19, wherein the ionic crosslinker is a metal salt selectedfrom the group consisting of aluminum acetylacetonate, ironacetylacetonate, zinc acetylacetonate, titanium acetylacetonate andzirconium acetylacetonate, aluminum triacetate, aluminium diacetate,aluminium monoacetate, tetra(2-ethylhexyl)titanate, and mixturesthereof.
 21. The gel of claim 14, wherein the crosslinker is an aminecrosslinker selected from the group consisting of ethylene diamine; 1,2-and 1,3-propylene diamine; 1,4-diaminobutane; 2,2-dimethylpropanediamine-(1,3); 1,6-diaminohexane; 2,5-dimethylhexane diamine-(2,5);2,2,4-trimethylhexane diamine-(1,6); 1,8-diaminooctane;1,10-diaminodecane; 1,11-undecane diamine; 1,12-dodecane diamine;1-methyl-4-(aminoisopropyl)-cyclohexylamine-1;3-aminomethyl-3,5,5-trimethyl-cyclohexylamine-(1);1,2-bis-(aminomethyl)-cyclobutane; p-xylylene diamine; 1,2- and1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin;1-methyl-4-aminoisopropyl-cyclohexylamine-1; 4,4′-diamino-dicyclohexyl;4,4′-diamino-dicyclohexyl methane;2,2′-(bis-4-amino-cyclohexyl)-propane;3,3′-dimethyl-4,4′-diamino-dicyclohexyl methane;1,2-bis-(4-aminocyclohexyl)-ethane;3,3′,5,5′-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane;1,4-bis-(2-aminoethyl)-benzene; benzidine; 4,4′-thiodianiline,dianisidine; 2,4-toluenediamine, diaminoditolylsulfone;2,6-diaminopyridine; 4-methoxy-6-methyl-m-phenylenediamine;diaminodiphenyl ether; 4,4′-bis(o-toluidine); o-phenylenediamine;o-phenylenediamine, methylenebis(o-chloroaniline);bis(3,4-diaminiophenyl)sulfone; diaminiodiphenylsulfone;4-chloro-o-phenylenediamine; m-aminobenzylamine; m-phenylenediamine;4,4′-methylenedianiline; aniline-formaldehyde resin; trimethylene glycoldi-p-aminobenzoate; bis-(2-aminoethyl)-amine; bis-(3-aminopropyl)-amine;bis-(4-aminobutyl)-amine; bis-(6-aminohexyl)-amine; isomeric mixtures ofdipropylene triamine and dibutylene triamine; and mixtures thereof. 22.The gel of claim 14, wherein the crosslinker is a polyol crosslinkerselected from the group consisting of 1,2-propanediol, 1,3-propanediol,diethanolamine, triethanolamine,N,N,N′,N′-[tetrakis(2-hydroxyethyl)ethylene diamine],N,N,-diethanolaniline, polycaprolactone diol, poly(propylene glycol),poly(ethylene glycol), poly(tetramethylene glycol), and polybutadienediol and their derivatives or copolymers, and mixtures thereof.
 23. Thegel of claim 14, wherein the base polymer comprises a styrenic blockcopolymer.
 24. The gel of claim 23, wherein the styrenic block copolymeris a styrene-ethylene/butylene-styrene orstyrene-ethylene/propylene-styrene copolymer.
 25. The gel of claim 14,wherein the base polymer comprises a maleated base polymer.
 26. The gelof claim 14, wherein the functionalized extender comprises a singleolefin at a terminal position on the extender.
 27. The gel of claim 14,wherein the functionalized extender is a polyisobutylene.
 28. The gel ofclaim 14, wherein the functionalized extender is a maleated extender.29. The gel of claim 28, wherein the maleated extender is a maleatedpolyisobutylene.
 30. The gel of claim 14, wherein the gel comprises oneor more of the following properties: a) a hardness between 80 g and 300g; b) a stress relaxation between 20% and 65% when the gel is subjectedto a deformation of 50% of its original size; c) a compression setbetween 4% and 20% after 50% strain has applied to the gel for 1000hours at 70° C.; and d) less than 10% oil bleed out after being undercompression of 1.2 atm for 60 days at 60° C.
 31. A closure orinterconnect system, comprising: a housing, a cable, and a hybridthermoplastic gel made by reacting: a functionalized extender, and abase polymer having at least one functional group capable ofcrosslinking.
 32. The system of claim 31, wherein the gel furthercomprises a crosslinker having multiple functional groups that arecompatible and willing to react with the functional groups in the basepolymer or functionalized extender.
 33. The system of claim 31, whereinthe gel is compatible with a LSZH cable as determined by a pressure losstest or tightness test following at least one of the followingmechanical or environmental tests: axial tension test, flexure test,re-entry test, torsion test, resistance to aggressive media test,resistance to stress cracking test, salt fog test, temperature cyclingtest, and waterhead test.
 34. The system of claim 31, further comprisinga connector and a receptacle for the connector.
 35. The system of claim31, wherein the gel has less than 10% oil bleed out after being undercompression of 1.2 atm for 60 days at 60° C.
 36. The system of claim 31,wherein the gel has less than 5% oil bleed out after being undercompression of 1.2 atm for 60 days at 60° C.
 37. A telecommunicationsapparatus comprising: a telecommunications component; and a sealant thatforms a seal with the telecommunications component, the sealant having afirst range of elongation followed by a second range of elongation, thesealant having a stress-strain profile having a first stress-strainslope corresponding to the first range of elongation and a secondstress-strain slope corresponding to the second range of elongation, thesecond stress-strain slope being steeper than the first stress-strainslope.
 38. The telecommunications apparatus of claim 37, wherein thetelecommunications component is a cable.
 39. The telecommunicationsapparatus of claim 37, wherein the telecommunications componentcomprises a housing.
 40. A sealant comprising: a sealant material havinga first range of elongation followed by a second range of elongation,the sealant material having a stress-strain profile having a firststress-strain slope corresponding to the first range of elongation and asecond stress-strain slope corresponding to the second range ofelongation, the second stress-strain slope being steeper than the firststress-strain slope.
 41. An enclosure comprising: a housing defining anopening; a sealant arrangement positioned within the opening of thehousing, the sealant arrangement defining at least one cable port, thesealant arrangement including a sealant material having a first range ofelongation followed by a second range of elongation, the sealantmaterial having a stress-strain profile having a first stress-strainslope corresponding to the first range of elongation and a secondstress-strain slope corresponding to the second range of elongation, thesecond stress-strain slope being steeper than the first stress-strainslope; and an actuation arrangement for pressurizing the sealantmaterial within the opening of the housing.
 42. The enclosure of claim41, wherein the actuation arrangement includes a spring for pressurizingthe sealant material.